In situcell-scale probing nucleation, growth and evolution of CsPbBr3nanowires by optical absorption spectroscopy.

The growth kinetics of colloidal lead halide perovskite nanomaterials are an integral part of their applications, remains poorly understood due to complex nucleation processes and lack ofin situsize monitoring method. Here we demonstrated that absorption spectra can be used to observein situgrowth processes of ultrathin CsPbBr3nanowires in solution with reference to the effective mass infinite deep square potential well model. By means of this method, we have found that the ultrathin nanowires, fabricated by hot injection method, were firstly formed within one minute. Subsequently, they merge with each other into a thicker structure with increasing reaction time. We revealed that the nucleation, growth, and merging of the CsPbBr3nanowires are determined by the acid concentration and ligand chain length. At lower acidity, the critical nucleation size of the nanowire is smaller, while the shorter the ligand chain length, the faster the merging among the nanowires. Moreover, the merging mode between nanowires changed with their nucleation size. This growth kinetics of CsPbBr3nanowires provides a reference for optimizing the synthesis conditions to obtain the one-dimensional CsPbBr3with desired size, thus enabling accurate control of the nanowire shape.

Edge optical scattering of two-dimensional materials.

Rayleigh scattering has shown powerful abilities to study electron resonances of nanomaterials regardless of the specific shapes. In analogy to Rayleigh scattering, here we demonstrate that edge optical scattering from two-dimensional(2D) materials also has the similar advantage. Our result shows that, in visible spectral range, as long as the lateral size of a 2D sample is larger than 2 µm, the edge scattering intensity distribution of the high-angle scattering in k space is nearly independent of the lateral size and the shape of the 2D samples. The high-angle edge scattering spectra are purely determined by the intrinsic dielectric properties of the 2D materials. As an example, we experimentally verify this feature in single-layer MoS2, in which A and B excitons are clearly detected in the edge scattering spectra, and the scattering images in k space and real space are consistent with our theoretical model. This study shows that the edge scattering is a highly practical and efficient method for optical studies of various 2D materials as well as thin films with clear edges.

Interfacially Al-doped ZnO nanowires: greatly enhanced near band edge emission through suppressed electron-phonon coupling and confined optical field.

Aluminium (Al)-doped zinc oxide (ZnO) nanowires (NWs) with a unique core-shell structure and a Δ-doping profile at the interface were successfully grown using a combination of chemical vapor deposition re-growth and few-layer AlxOy atomic layer deposition. Unlike the conventional heavy doping which degrades the near-band-edge (NBE) luminescence and increases the electron-phonon coupling (EPC), it was found that there was an over 20-fold enhanced NBE emission and a notably-weakened EPC in this type of interfacially Al-doped ZnO NWs. Further experiments revealed a greatly suppressed nonradiative decay process and a much enhanced radiative recombination rate. By comparing the finite-difference time-domain simulation with the experimental results from intentionally designed different NWs, this enhanced radiative decay rate was attributed to the Purcell effect induced by the confined and intensified optical field within the interfacial layer. The ability to manipulate the confinement, transport and relaxation dynamics of ZnO excitons can be naturally guaranteed with this unique interfacial Δ-doping strategy, which is certainly desirable for the applications using ZnO-based nano-photonic and nano-optoelectronic devices.

Near-infrared quarter-waveplate with near-unity polarization conversion efficiency based on silicon nanowire array.

Metasurfaces made of subwavelength resonators can modify the wave front of light within the thickness much less than free space wavelength, showing great promises in integrated optics. In this paper, we theoretically show that electric and magnetic resonances supported simultaneously by a subwavelength nanowire with high refractive-index can be utilized to design metasurfaces with near-unity transmittance. Taking silicon nanowire for instance, we design numerically a near-infrared quarter-waveplate with high transmittance using a subwavelength nanowire array. The operation bandwidth of the waveplate is 0.14 µm around the center wavelength of 1.71 µm. The waveplate can convert a 45° linearly polarized incident light to circularly polarized light with conversion efficiency ranging from 94% to 98% over the operation band. The performance of quarter waveplate can in principle be tuned and improved through optimizing the parameters of nanowire arrays. Its compatibility to microelectronic technologies opens up a distinct possibility to integrate nanophotonics into the current silicon-based electronic devices.

Negative thermal quenching of photoluminescence in annealed ZnO-Al2O3 core-shell nanorods.

ZnO-Al2O3 core-shell nanorods (NRs) have been fabricated through the vapor phase condensation method and atomic layer deposition. It is found that the nanorod comprises a wurtzite single crystalline ZnO core with the main axes along the [0001] direction and an amorphous Al2O3 shell. The temperature-dependent photoluminescence (PL) properties of the as-grown and annealed ZnO/Al2O3 NRs are investigated systematically. The PL of the as-grown ZnO/Al2O3 NRs demonstrates a normal thermal quenching feature. However, the salient behavior of negative thermal quenching (NTQ), i.e., the increase in PL intensity with an increase in temperature, is clearly observed in the annealed ZnO/Al2O3 NRs. A multi-level model is adopted to account for this behavior and the thermal activation energy of the NTQ process is estimated to be ∼69 meV. Moreover, we suggest that the activation energy is related to the Al donor defect in ZnO resulting from the inter-diffusion between the ZnO core and the Al2O3 shell during the annealing process.

Realizing full visible spectrum metamaterial half-wave plates with patterned metal nanoarray/insulator/metal film structure.

Abrupt phase shift introduced by plasmonic resonances has been frequently used to design subwavelength wave plates for optical integration. Here, with the sandwich structure consisting of a top periodic patterned silver nanopatch, an in-between insulator layer and a bottom thick Au film, we realize a broadband half-wave plate which is capable to cover entire visible light spectrum ranging from 400 to 780 nm. Moreover, when the top layer is replaced with a periodic array of composite super unit cell comprised of two nanopatches with different sizes, the operation bandwidth can be further improved to exceed an octave (400-830 nm). In particular, we demonstrate that the designed half-wave plate can be used efficiently to rotate the polarization state of an ultra-fast light pulse with reserved pulse width. Our result offers a new strategy to design and construct broadband high efficiency phase-response based optical components using patterned metal nanoarray/insulator/metal structure.

Deep Blue CsPbBr3 Quantum Wires with Tailored Shapes.

Low-dimension metal halide perovskites are attractive for bandgap tunable optoelectronic materials. Among them, 1-D CsPbBr3 quantum wires (QWs) are emerging as promising deep-blue luminescent material. However, the growth dynamics of 1-D perovskite QWs are intricate, making the study and control of 1-D QWs highly challenging. In this study, a strategy for controlling both the length and width of the CsPbBr3 QWs was realized. The temperature-dependent isotropic growth mechanism was revealed and employed as the main tool for the oriented growth of 1-D CsPbBr3 QWs for various aspect ratios. Our results pave the way for the controlled synthesis of ultrasmall perovskite nanocrystals.

Tailoring the coupling between localized and propagating surface plasmons: realizing Fano-like interference and high-performance sensor.

Surface plasmon modes originated from various metallic nanostructures possess unique features of strong nanoscale light confinement and enhancement with tunable energy, which make them attractive and promising for a variety of applications such as sensing, solar cell, and lasing. Here, we have investigated the interaction between localized and propagating surface plasmons in a structure consisting of a gold nanobar array and a thick gold film, separated by a silica dielectric spacer layer. It is found that the reflection spectrum of the designed plasmonic structure can be readily tailored by changing the gold nanobar size, array period and the spacer layer thickness. Moreover, the strong coupling between the localized and propagating modes can result in an anticrossing behavior and even induce a Fano-like asymmetric lineshape. Importantly, the sensitivity and the figure of merit (FoM) of this plasmonic system can reach as high as 936 nm/RIU and 112, respectively. Our study offers a new, simple, efficient and controllable way to design the plasmonic systems with desired modes coupling and spectral lineshapes for different applications.

Enhanced Organic Thin-Film Transistor Stability by Preventing MoO3 Diffusion with Metal/MoO3/Organic Multilayered Interface Source-Drain Contact.

The source-drain electrode with a MoO3 interfacial modification layer (IML) is considered the most promising method to solve electrical contact issues impeding organic thin-film transistors (OTFTs) from commercialization. However, this method raises many concerns because MoO3 might diffuse into organic materials, which causes device instability. In this work, we observed a significant device stability degradation by damaging on/off switching performance caused by MoO3 diffusion. To prevent the MoO3 diffusion, a source-drain electrode with a multilayered interface contact (MIC) consisting of a top-down stack of metal, MoO3 IML, and organic buffer layer (OBL) is proposed. In the MIC device, the MoO3 IML serves well for its intended functions of reducing contact resistance and suppressing minority carrier injection to the OTFT channel. The inclusion of OBL to the MIC helps block MoO3 diffusion and thereby leads to better device stability and an increased on/off ratio. Through combinations with several organic compounds as a buffer layer, the MoO3 diffusion related electrical behaviors of OTFTs are systematically studied. Key parameters related to MoO3 diffusion such as the Fick coefficient and bias-stress stability such as carrier trapping time are extracted from numerical device analysis. Finally, we summarize a general rule of material selection for making robust source-drain contact.

In Situ Low-Temperature Growth and Superior Luminescent Property of Well-Aligned, High-Quality Cubic CsPbBr3 Micrometer-Scale Single Crystal Arrays on Transparent Conductive Substrates.

Direct assembly of high-quality single-crystal perovskite microarrays on transparent conductive substrates and carrier injection layers is vital to realize high-performance optoelectronic devices. Although cubic-phase CsPbBr3 is considered to have a higher structural and optical quality than the orthorhombic one, obtaining a well-aligned assembly directly on the aforementioned substrates is still challenging. Here we developed a solvent-assisted crystallization strategy with the assistance of surface modifiers, through which the in situ low-temperature growth of well-aligned cubic single-crystal CsPbBr3 microarray with a preferential out-of-plane [100] orientation is achieved for the first time on commercial transparent conductive substrates. As compared with the control orthorhombic samples, the cubic CsPbBr3 single crystals possess superior properties including a higher photoluminescence internal quantum efficiency, fewer defect states, a weaker scattering by phonons, and an appearance of lasing. The results presented here can pave the way for future design and applications of optoelectronic devices based on perovskite microarrays.

Broadband absorption enhancement achieved by optical layer mediated plasmonic solar cell.

We propose a novel thin solar cell design, integrating plasmonic component with optical layer, for conspicuous performance improvement in organic (P3HT: PCBM) thin film solar cell. Despite the relatively simple structure, the designed solar cell can get strikingly high spectral performance with the short circuit current density (J(sc)) enhancement up to 67%; and a nicely large J(sc) enhancement over 50% can be easily obtained spanning rather a broad geometric parametric range. The mechanisms responsible for this significant and broadband absorption enhancement as well as the effects of intercalating a plasmonic nanoparticles (NPs) array and an optical layer are theoretically and systematically investigated by finite-difference time-domain calculations (FDTD). The origin of the dramatically increased absorption is believed to be the synergistic effect between 1) the enhanced electric field and forward scattering upon excitation of localized surface plasmon resonance (LSPR) of the NPs, and 2) the favorable redistributions of light field in the device due to the beneficial interference effect mediated by the optical layer. Such a design concept is quite versatile and can be easily extended to other thin film solar cell systems.

Realizing CsPbBr3 Light-Emitting Diode Arrays Based on PDMS Template Confined Solution Growth of Single-Crystalline Perovskite.

Metal-halide perovskites have shown excellent optoelectronic properties, among which the array-type architecture is highly desirable. However, both the susceptibility of perovskites to polar solvents and the complex 3D geometry of array structure have led to great challenges for device fabrication and performance, which hinders their further applications. Here, we report a simple but efficient approach highly compatible with the state-of-the-art microelectronics processes to construct single-crystalline array light-emitting diodes (LEDs) of perovskite. The well-aligned single-crystalline array was sandwiched as the emission layer, among the carefully designed multilayer ITO/NiO/CsPbBr3/PMMA/ZnO/Ag structure. Through systematically altering the size of CsPbBr3 single crystal and the thickness of insulation layer, the device performance has been optimized and eventually achieved a 99% working ratio in a 62 × 47 array. Moreover, a prototype device of LED display was also fabricated. These results clearly demonstrate that our strategy is efficient, reliable, and versatile, which can be easily extended to other perovskites.

Fabricating 3D Metastructures by Simultaneous Modulation of Flexible Resist Stencils and Basal Molds.

Metamaterials have gained much attention thanks to their extraordinary and intriguing optical properties beyond natural materials. However, universal high-resolution fabrications of 3D micro/nanometastructures with high-resolution remain a challenge. Here, a novel approach to fabricate sophisticated 3D micro/nanostructures with excellent robustness and precise controllability is demonstrated by simultaneously modulating of flexible resist stencils and basal molds. This method allows arbitrary manipulations of morphology, size, and orientation, as well as contact angles of the objects. Combined with a new alignment strategy of high-resolution, previously inaccessible architectures are fabricated with ultrahigh precision, leading to an excellent spectra response from the fabricated metastructures. This method provides a new possibility to realize true 3D metamaterial fabrications featuring high-resolution and direct-compatibility with broad planar lithography platforms.

Fabrication of Low-Cost and Highly Sensitive Graphene-Based Pressure Sensors by Direct Laser Scribing Polydimethylsiloxane.

The cost-effective production of flexible interconnects is a challenge in epidermal electronics. Here we report a low-cost approach for producing and patterning graphene films from polydimethylsiloxane films by direct laser scribing in ambient air. The produced graphene films exhibit high electrical conductivity and excellent mechanical properties and can thus be used directly as a flexible conductive layer without the need for metals. The skinlike pressure sensor with these layers exhibits ultrahigh sensitivity (∼480 kPa-1) while maintaining the fast response/relaxation time (2 µs/3 µs) and excellent cycle stability (>4000 repetitive cycles). Moreover, it can naturally attach to the skin to monitor the wrist pulse. In addition, a 7 × 7 sensor array has been fabricated, which possesses the capability to detect the spatial distribution of pressure. This device has great potential for application in epidermal electronics because of its low cost and high performance.

Lattice Disorder-Engineered Energy Splitting between Bright and Dark Excitons in CsPbBr3 Quantum Wires.

Excitons in nanostructured semiconductors often undergo strong electron-hole exchange interaction, resulting in bright-dark exciton splitting with the dark exciton usually being the lower energy state. This unfavorable state arrangement has become the major bottleneck for achieving high photoluminescence quantum yield (PLQY). However, the arrangement of dark and bright exciton states in lead halide perovskites is under intense debate due to the involvement of many complicated factors. We present here the first experimental evidence to demonstrate that the strain is a crucial factor in tuning the energy splitting of the bright and dark excitons, resulting in different PL properties.

Probing Exciton Complexes and Charge Distribution in Inkslab-Like WSe2 Homojunction.

By virtue of the layer-dependent band structure and valley-selected optical/electronic properties, atomically layered transition-metal dichalcogenides (TMDs) exhibit great potentials such as in valleytronics and quantum devices, and have captured significant attentions. Precise control of the optical and electrical properties of TMDs is always the pursuing goal for real applications, and constructing advanced structures that allow playing with more degrees of freedom may hold the key. Here, we introduce a triangular inkslab-like WSe2 homojunction with a monolayer in the inner surrounded by a multilayer frame. Benefit from this interesting structure, the photoluminescence (PL) peaks redshift up to 50 meV and the charge density increases about 6 times from the center to the edge region of the inner monolayer. We demonstrated that the Se-deficient multilayer frame offers the excessive free electrons for the generation of the electron density gradient inside the monolayer, which also results in the spatial variation and distribution gradient of a series of exciton complexes. Furthermore, we observed the strong rectifying characteristic and clear photovoltaic response across the homojunction through measuring and mapping the photocurrent of the devices. Our result provides another route for efficient modulation of the exciton-complex emissions of TMDs, which is exceptionally desirable for the "layer- and charge-engineered" photonic and optoelectronic devices.

Efficient Energy Transfer in In2Se3-MoSe2 van der Waals Heterostructures.

We show that bilayer α-phase In2Se3 and monolayer MoSe2 form a type-I band alignment, with both the conduction band minimum and the valence band maximum located in MoSe2. Samples were fabricated by a two-step chemical vapor deposition method. The photoluminescence yield of the heterostructure sample was found to be similar to monolayer MoSe2, indicating the lack of an efficient charge transfer from MoSe2 to In2Se3. This is further confirmed by the observation that the photocarrier lifetime in the heterostructure is similar to monolayer MoSe2, showing the lack of layer separation of the electrons and holes. Efficient energy transfer from In2Se3 to MoSe2 was observed by the sevenfold enhancement of the differential reflection signal in the heterostructure and its ultrashort rising time. Furthermore, we observed significant photoluminescence quenching in heterostructures formed by bulk In2Se3 and monolayer MoSe2, which suggests efficient charge transfer and therefore type-II band alignment. These findings suggest that α-In2Se3 ultrathin layers can be effectively integrated as light-absorbing layers with other transition metal dichalcogenides for novel optoelectronic applications.

High-Throughput Fabrication of Ultradense Annular Nanogap Arrays for Plasmon-Enhanced Spectroscopy.

The confinement of light into nanometer-sized metallic nanogaps can lead to an extremely high field enhancement, resulting in dramatically enhanced absorption, emission, and surface-enhanced Raman scattering (SERS) of molecules embedded in nanogaps. However, low-cost, high-throughput, and reliable fabrication of ultra-high-dense nanogap arrays with precise control of the gap size still remains a challenge. Here, by combining colloidal lithography and atomic layer deposition technique, a reproducible method for fabricating ultra-high-dense arrays of hexagonal close-packed annular nanogaps over large areas is demonstrated. The annular nanogap arrays with a minimum diameter smaller than 100 nm and sub-1 nm gap width have been produced, showing excellent SERS performance with a typical enhancement factor up to 3.1 × 106 and a detection limit of 10-11 M. Moreover, it can also work as a high-quality field enhancement substrate for studying two-dimensional materials, such as MoSe2. Our method provides an attractive approach to produce controllable nanogaps for enhanced light-matter interaction at the nanoscale.

Utilization of Resist Stencil Lithography for Multidimensional Fabrication on a Curved Surface.

The limited ability to fabricate nanostructures on nonplanar rugged surfaces has severely hampered the applicability of many emerging technologies. Here we report a resist stencil lithography based approach for in situ fabrication of multidimensional nanostructures on both planar and uneven substrates. By using the resist film as a flexible stencil to form a suspending membrane with predesigned patterns, a variety of nanostructures have been fabricated on curved or uneven substrates of diverse morphologies on demand. The ability to realize 4 in. wafer scale fabrication of nanostructures as well as line width resolution of sub-20 nm is also demonstrated. Its extraordinary capacity is highlighted by the fabrication of three-dimensional wavy nanostructures with diversified cell morphologies on substrates of different curvatures. A robust general scheme is also developed to construct various complex 3D nanostructures. The use of conventional resists and processing ensures the versatility of the method. Such an in situ lithography technique has offered exciting possibilities to construct nanostructures with high dimensionalities that can otherwise not be achieved with existing nanofabrication methods.

Manipulating the quantum interference effect and magnetotransport of ZnO nanowires through interfacial doping.

We carefully prepared interfacial Al-doped (IAD) and interfacial natively-doped (IND) ZnO nanowires (NWs) by introducing atomic-layer interfacial Δ-doping between the two steps of CVD growth. Variable-temperature electron transport as well as magnetotransport behaviours of these NWs were systematically investigated. By virtue of the unique architecture and the quality-guaranteed growth technique, a series of quantum interference effects were clearly observed in the IAD ZnO NWs, including weak localization, universal conductance fluctuation and Altshuler-Aronov-Spivak oscillations. The phase-coherence length (Lφ) of electrons exceeds 100 nm in the IAD ZnO NWs, much longer than those in the IND ones and most conventionally doped ZnO NWs. This ability to efficiently manipulate a variety of quantum interference effects in ZnO NWs is very desirable for applications in nano-optoelectronics, nano- & quantum-electronics and solid-state quantum computing.